KR20100124761A - Lubricant composition - Google Patents

Lubricant composition Download PDF

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KR20100124761A
KR20100124761A KR1020107020361A KR20107020361A KR20100124761A KR 20100124761 A KR20100124761 A KR 20100124761A KR 1020107020361 A KR1020107020361 A KR 1020107020361A KR 20107020361 A KR20107020361 A KR 20107020361A KR 20100124761 A KR20100124761 A KR 20100124761A
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mass
lubricating oil
oil composition
oil
sulfur
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KR1020107020361A
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Korean (ko)
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가즈히로 데시마
모또하루 이시까와
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이데미쓰 고산 가부시키가이샤
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Publication of KR20100124761A publication Critical patent/KR20100124761A/en

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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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  • Chemical & Material Sciences (AREA)
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Abstract

본 발명의 윤활유 조성물은 천연 유지, 천연 유지의 수소화 처리물, 천연 유지의 에스테르 교환물 및 천연 유지의 에스테르 교환물의 수소화 처리물 중으로부터 선택된 적어도 1종을 포함하는 연료를 사용하는 내연 기관에서 사용되는 윤활유 조성물이며, 기유에 -C-S-C- 결합을 적어도 하나 포함하는 황 화합물이 배합되고, 상기 -C-S-C- 결합에 포함되는 황이 조성물 전량 기준으로 0.3 질량％ 이하이다.The lubricating oil composition of the present invention is used in an internal combustion engine using a fuel comprising at least one selected from natural fats and oils, a hydrogenated treatment of natural fats and oils, a transesterification of natural fats and oils, and a hydrogenated treatment of a transesterification of natural fats and oils. It is a lubricating oil composition, The sulfur compound which contains at least 1 -CSC- bond in a base oil is mix | blended, and sulfur contained in the said -CSC- bond is 0.3 mass% or less based on the whole composition.

Description

윤활유 조성물{LUBRICANT COMPOSITION}Lube oil composition {LUBRICANT COMPOSITION}

본 발명은 천연 유지에서 유래하는 연료를 사용하는 내연 기관에 사용되는 윤활유 조성물에 관한 것이다.The present invention relates to a lubricating oil composition for use in an internal combustion engine using a fuel derived from natural fats and oils.

현재, 지구 규모에서의 환경 규제는 더욱 엄격해지고 있으며, 특히 자동차를 둘러싼 상황은 연비 규제, 배기 가스 규제 등 더욱 엄격해지고 있다. 그 배경에는 지구 온난화 등의 환경 문제와, 석유 자원의 고갈에 대한 염려로 인한 자원 보호가 있다.Currently, environmental regulations on the global scale are becoming more stringent, especially the situation surrounding automobiles is becoming more stringent, such as fuel economy regulation and exhaust gas regulation. The background is environmental protection such as global warming and resource protection due to concerns about the depletion of oil resources.

한편, 지구상에 존재하는 식물은 대기 중의 이산화탄소, 물 및 태양광을 흡수하고 광합성을 행하여, 탄수화물 및 산소를 생성한다. 그 때문에, 식물을 원료로 한 식물유로 제조되는 소위 바이오 연료는, 지구 온난화의 주된 요인인 이산화탄소의 삭감, 나아가서는 자동차로부터 배출되는 대기 오염 물질의 감소 효과 등의 면에서 크게 주목받고 있다. 또한, 식물 바이오매스의 연소에 의해 생성되는 이산화탄소는 지구 온난화 가스의 증가에 계산되지 않는 탄소 중립(carbon neutral)이라는 견해도 있기 때문에, 향후 탄화수소계 연료에 대한 바이오 연료의 혼합 비율은 증가할 것으로 예상된다(예를 들면, 비특허문헌 1 참조).On the other hand, plants present on earth absorb carbon dioxide, water and sunlight in the atmosphere and perform photosynthesis to produce carbohydrates and oxygen. For this reason, so-called biofuels produced from vegetable oils based on plants have attracted much attention in terms of reducing carbon dioxide, which is a major factor of global warming, and reducing air pollutants emitted from automobiles. In addition, since there is a view that carbon dioxide produced by the combustion of plant biomass is carbon neutral, which is not calculated by the increase in global warming gas, the mixing ratio of biofuel to hydrocarbon fuel is expected to increase in the future. (For example, refer nonpatent literature 1).

야마네 코지 저 "바이오디젤 튀김 냄비로부터 연료 탱크로" 도꾜 도서 출판회, 2006년 5월 발행 By Yamane Koji "Biodiesel frying pan to fuel tank" Tokyo book publication, May 2006 issuance

내연 기관, 특히 디젤 엔진에 있어서는, 그을음 등의 입자상 물질(PM)이나 NOx 등의 배출 가스 성분에 의한 환경오염을 경감시키기 위한 대책이 중요한 과제가 되었다. 그 대책으로서는, 자동차에 디젤 미립자 필터(DPF)나 배출 가스 정화 촉매(산화 또는 환원 촉매) 등의 배출 가스 정화 장치를 장착하는 것이 유효하다. 예를 들면, 디젤 엔진에서 생성된 그을음은 DPF에 부착된 후, 산화, 연소에 의해 제거된다.In internal combustion engines, especially diesel engines, measures to reduce environmental pollution caused by particulate matter (PM) such as soot and exhaust gas components such as NO x have become an important problem. As a countermeasure, it is effective to equip an automobile with exhaust gas purification apparatuses, such as a diesel particulate filter (DPF) and an exhaust gas purification catalyst (oxidation or a reduction catalyst). For example, soot produced in diesel engines is attached to the DPF and then removed by oxidation and combustion.

여기서, 디젤 엔진에 DPF를 장착한 경우, 필터에 축적된 그을음을 연소시키기 위해 일반적으로 연료의 포스트 분사가 행해지고 있다. 이 포스트 분사에 의해 엔진유에 대한 연료 희석이 증대되어, 엔진유 성능의 저하가 예상된다. 특히 바이오 연료는 그의 물성으로 인해 엔진유에 축적되기 쉽고, 바이오 연료가 열화 분해되었을 때 극성 화합물이 발생하기 때문에, 엔진 부품(피스톤 등)의 부식에 악영향이 크다. 또한, 연소에 의해 생성된 금속 산화물이나 황산염, 카르복실산염 등에 의해 필터가 클로깅되기 쉽다는 문제점도 있다. 또한, 사용된 엔진유의 일부는 연소되어 배출 가스로서 배출되기 때문에, 윤활유 중의 금속 성분이나 황 성분은 가능한 한 낮게 하는 것이 바람직하다. 그 때문에, 윤활유 중의 인 성분 및 황 성분을 감소시키는 것은 배출 가스 정화 촉매의 열화 대책면에서도 바람직하다.Here, in the case where the DPF is attached to the diesel engine, post injection of fuel is generally performed to burn the soot accumulated in the filter. This post-injection increases fuel dilution with respect to engine oil, and the fall of engine oil performance is anticipated. In particular, biofuels tend to accumulate in engine oil due to their physical properties, and since polar compounds are generated when biofuels deteriorate and decompose, they have a bad influence on corrosion of engine parts (such as pistons). There is also a problem that the filter is easily clogged by metal oxides, sulfates, carboxylates, and the like produced by combustion. In addition, since part of the used engine oil is combusted and discharged as exhaust gas, it is preferable to keep the metal component and sulfur component in the lubricating oil as low as possible. Therefore, it is preferable to reduce the phosphorus component and sulfur component in the lubricating oil in view of the deterioration countermeasure of the exhaust gas purification catalyst.

그러나, 현재까지 바이오 연료에 적합한 윤활유는 제공되지 않았다. 예를 들면, 단순히 윤활유 중의 금속 성분, 인 성분 또는 황 성분 등의 함유량을 적게 하면, 오히려 윤활성을 손상시킬 염려도 있다. 특히 바이오 연료는 상기한 바와 같이 연료 자체가 열화 분해되었을 때 극성 화합물이 발생하기 때문에, 엔진 부품을 부식시키기 쉽다는 문제점이 있다.However, no lubricants suitable for biofuels have been provided to date. For example, simply reducing the content of the metal component, phosphorus component, sulfur component and the like in the lubricating oil may rather impair lubricity. In particular, the biofuel has a problem in that it is easy to corrode engine parts because polar compounds are generated when the fuel itself is thermally decomposed as described above.

따라서, 본 발명의 주된 목적은, 바이오 연료나 바이오 연료를 혼합한 연료를 디젤 엔진 등의 내연 기관에 사용하여도 엔진 부품에 대한 부식의 영향이 적은 윤활유 조성물을 제공하는 것에 있다.Accordingly, a main object of the present invention is to provide a lubricating oil composition having less influence of corrosion on engine parts even when a fuel containing biofuel or biofuel is used in an internal combustion engine such as a diesel engine.

본 발명은, 상기한 과제를 해결하기 위해 이하에 나타내는 윤활유 조성물을 제공하는 것이다.MEANS TO SOLVE THE PROBLEM This invention provides the lubricating oil composition shown below in order to solve the said subject.

(1) 천연 유지, 천연 유지의 수소화 처리물, 천연 유지의 에스테르 교환물 및 천연 유지의 에스테르 교환물의 수소화 처리물 중으로부터 선택된 적어도 1종을 포함하는 연료를 사용하는 내연 기관에서 사용되는 윤활유 조성물이며, 기유에 -C-S-C- 결합을 적어도 하나 포함하는 황 화합물이 배합되고, 상기 -C-S-C- 결합에 포함되는 황이 조성물 전량 기준으로 0.3 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.(1) a lubricating oil composition for use in an internal combustion engine using a fuel comprising at least one selected from natural fats and oils, a hydrogenated oil of natural fats, a transesterified oil of natural fats, and a hydrogenated water of transesterified natural fats and oils; And a sulfur compound containing at least one -CSC- bond in a base oil, wherein the sulfur contained in the -CSC- bond is 0.3% by mass or less based on the total amount of the composition.

(2) 상술한 본 발명의 윤활유 조성물에 있어서, 상기 황 화합물이 -C-Sx-C- 결합(x는 2 이상의 정수임)을 포함하지 않는 것을 특징으로 하는 윤활유 조성물.(2) The lubricating oil composition of the lubricating oil composition of the present invention described above, wherein the sulfur compound does not contain a -CS x -C- bond (x is an integer of 2 or more).

(3) 상술한 본 발명의 윤활유 조성물에 있어서, 알칼리 토류 금속계 청정제가 0.35 질량％ 이하 배합되어 있는 것을 특징으로 하는 윤활유 조성물.(3) In the lubricating oil composition of the present invention described above, 0.35% by mass or less of an alkaline earth metal-based detergent is blended.

(4) 상술한 본 발명의 윤활유 조성물에 있어서, 인 함유량이 조성물 기준으로 0.12 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.(4) The lubricating oil composition of the present invention described above, wherein the phosphorus content is 0.12% by mass or less based on the composition.

(5) 상술한 본 발명의 윤활유 조성물에 있어서, 황산 회분이 1.1 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.(5) The lubricating oil composition of the lubricating oil composition of the present invention described above, wherein the sulfuric acid ash content is 1.1% by mass or less.

(6) 상술한 본 발명의 윤활유 조성물에 있어서, 페놀계 산화 방지제 및/또는 아민계 산화 방지제를 조성물 전량 기준으로 0.3 질량％ 이상 배합하는 것을 특징으로 하는 윤활유 조성물.(6) The lubricating oil composition of the present invention described above, wherein the phenolic antioxidant and / or the amine antioxidant are blended in an amount of 0.3% by mass or more based on the total amount of the composition.

(7) 상술한 본 발명의 윤활유 조성물에 있어서, 황 함유량이 조성물 전량 기준으로 0.5 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.(7) The lubricating oil composition of the lubricating oil composition of the present invention described above, wherein the sulfur content is 0.5% by mass or less based on the total amount of the composition.

본 발명의 윤활유 조성물에 따르면, 천연 유지 등을 포함하는 소위 바이오 연료를 사용하는 내연 기관에서 엔진유 중에 바이오 연료가 혼입되어도, 피스톤 등의 엔진 부품에 대하여 부식성을 나타내는 경우가 거의 없다. 또한, 본 발명의 윤활유 조성물에서는 DPF에 잔존하는 회분을 적게 할 수 있기 때문에, DPF 장착 디젤 엔진에 사용하는 경우에도 DPF의 성능 저하를 일으키지 않는다.According to the lubricating oil composition of the present invention, even when biofuel is mixed in the engine oil in an internal combustion engine using a so-called biofuel containing natural oils and the like, it hardly exhibits corrosion to engine parts such as pistons. In addition, in the lubricating oil composition of the present invention, since the ash remaining in the DPF can be reduced, the performance of the DPF is not deteriorated even when used in a diesel engine equipped with the DPF.

또한, 본 발명에서의 천연 유지는 식물 기원인 것으로 한정되지 않으며, 동물 기원인 것도 포함된다.In addition, the natural fats and oils in this invention are not limited to being of plant origin, but also the thing of animal origin.

이하, 본 발명에 대하여 실시 형태를 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, embodiment is described in detail about this invention.

본 발명은 천연 유지, 천연 유지의 수소화 처리물, 천연 유지의 에스테르 교환물 및 천연 유지의 에스테르 교환물의 수소화 처리물 중으로부터 선택된 적어도 1종을 포함하는 연료를 사용하는 내연 기관에서 사용되는 윤활유 조성물이다.The present invention is a lubricating oil composition for use in an internal combustion engine using a fuel comprising at least one selected from natural oils, hydrogenated natural oils, transesterified natural oils and hydrogenated natural oils. .

여기서, 천연 유지로서는, 천연계에 폭넓게 존재하는 각종 동식물 유지를 사용할 수 있지만, 지방산과 글리세린의 에스테르를 주성분으로 하는 식물유, 예를 들면 홍화유, 대두유, 채종유, 팜유, 팜핵유, 면실유, 야자유, 미강유, 호마유, 피마자유, 아마인유, 올리브유, 동유, 동백유, 낙화생유, 케이폭유, 카카오유, 목랍, 해바라기유, 콘유 등이 바람직하게 사용된다.Here, as natural fats and oils, various animal and vegetable fats and oils which exist widely in nature can be used, but vegetable oils based on esters of fatty acids and glycerin, such as safflower oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, cottonseed oil, palm oil, rice bran oil, Homa oil, castor oil, linseed oil, olive oil, copper oil, camellia oil, peanut oil, kapok oil, cacao oil, wax, sunflower oil, corn oil and the like are preferably used.

천연 유지의 수소화 처리물이란, 상기한 유지를 적당한 수소화 촉매의 존재하에 소위 수소 첨가한 것이다.The hydrogenated product of natural fats and oils is what adds the said fats and oils in presence of a suitable hydrogenation catalyst, so-called hydrogenation.

여기서, 수소화 촉매로서는 니켈계 촉매, 백금족(Pt, Pd, Rh, Ru)계 촉매, 코발트계 촉매, 산화 크롬계 촉매, 구리계 촉매, 오스뮴계 촉매, 이리듐계 촉매, 몰리브덴계 촉매 등을 들 수 있다. 또한, 수소화 촉매로서는 상기 촉매를 2개 이상 조합하여 사용하는 것도 바람직하다.Here, examples of the hydrogenation catalyst include nickel catalysts, platinum group (Pt, Pd, Rh, Ru) catalysts, cobalt catalysts, chromium oxide catalysts, copper catalysts, osmium catalysts, iridium catalysts, and molybdenum catalysts. have. Moreover, as a hydrogenation catalyst, it is also preferable to use combining two or more said catalysts.

천연 유지의 에스테르 교환물이란, 적당한 에스테르 합성 촉매의 존재하에 천연 유지를 구성하는 트리글리세리드에 대하여 에스테르 교환 반응을 행하여 얻어진 에스테르이다. 예를 들면, 저급 알코올과 유지를 상기 에스테르 합성 촉매의 존재하에 에스테르 교환 반응시킴으로써, 바이오 연료가 되는 지방산 에스테르가 제조된다. 저급 알코올은 에스테르화제로서 사용되는 것이며, 메탄올, 에탄올, 프로판올, 부탄올, 펜탄올 등의 탄소수 5 이하의 알코올을 들 수 있지만, 반응성의 면이나 비용의 면에서도 메탄올이 바람직하다. 이러한 저급 알코올은, 일반적으로 유지에 대하여 당량 이상의 양으로 사용된다.The transesterification product of a natural fat or oil is ester obtained by transesterification with respect to the triglyceride which comprises a natural fat or oil in presence of a suitable ester synthesis catalyst. For example, a fatty acid ester to be a biofuel is produced by transesterifying a lower alcohol with an oil or fat in the presence of the ester synthesis catalyst. Lower alcohols are used as esterification agents, and alcohols having 5 or less carbon atoms, such as methanol, ethanol, propanol, butanol and pentanol, are mentioned, but methanol is also preferable in terms of reactivity and cost. Such lower alcohols are generally used in amounts equivalent to or greater than fats and oils.

또한, 천연 유지의 에스테르 교환물의 수소화 처리물이란, 상기한 에스테르 교환물을 적당한 수소화 촉매의 존재하에 수소 첨가한 것이다.In addition, the hydroprocessing product of the transesterification of natural fats and oils is hydrogenated said transesterification in presence of a suitable hydrogenation catalyst.

천연 유지, 천연 유지의 수소화 처리물, 천연 유지의 에스테르 교환물 및 천연 유지의 에스테르 교환물의 수소화 처리물은, 경유 등의 탄화수소로 구성되는 연료에 첨가함으로써 혼합 연료로서도 바람직하게 사용할 수 있다.The natural fats and oils, the hydroprocessed natural fats, the transesterified natural fats, and the hydrogenated product of the transesterified natural fats can be preferably used as a mixed fuel by adding it to a fuel composed of hydrocarbons such as light oil.

본 발명의 윤활유 조성물에 사용되는 기유로서는 특별히 제한은 없으며, 종래 내연 기관용 윤활유의 기유로서 사용된 광유나 합성유 중으로부터 임의의 것을 적절하게 선택하여 사용할 수 있다.There is no restriction | limiting in particular as base oil used for the lubricating oil composition of this invention, Arbitrary thing can be suitably selected from the mineral oil or synthetic oil conventionally used as base oil of the lubricating oil for internal combustion engines.

광유로서는, 예를 들면 원유를 상압 증류하여 얻어지는 상압 잔유를 감압 증류하여 얻어진 윤활유 증류분을, 용제 탈력(solvent-deasphalting), 용제 추출, 수소화 분해, 용제 탈랍, 접촉 탈랍, 수소화 정제 등 중 하나 이상의 처리를 행하여 정제한 광유, 또는 왁스, GTL(가스 액화, Gas-To-Liquid) 왁스를 이성화(異性化)함으로써 제조되는 광유 등을 들 수 있다.As mineral oil, the lubricating oil distillate obtained by distilling under reduced pressure the atmospheric residual oil obtained by atmospheric distillation of crude oil, for example, is one or more of solvent-deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc. Mineral oil or the wax refined by treatment, and mineral oil produced by isomerizing GTL (Gas-To-Liquid) wax.

한편, 합성유로서는, 예를 들면 폴리부텐, 폴리올레핀[α-올레핀 단독 중합체나 공중합체(예를 들면, 에틸렌-α-올레핀 공중합체) 등], 각종 에스테르(예를 들면, 폴리올에스테르, 이염기산에스테르, 인산에스테르 등), 각종 에테르(예를 들면, 폴리페닐에테르 등), 폴리글리콜, 알킬벤젠, 알킬나프탈렌 등을 들 수 있다. 이들 합성유 중, 특히 폴리올레핀, 폴리올에스테르가 바람직하다.On the other hand, as synthetic oil, for example, polybutene, polyolefin [alpha-olefin homopolymer or copolymer (for example, ethylene-alpha-olefin copolymer), etc.), various esters (for example, polyol ester, dibasic acid ester) , Phosphate esters, and the like), various ethers (for example, polyphenyl ether, etc.), polyglycol, alkylbenzene, alkylnaphthalene, and the like. Among these synthetic oils, polyolefins and polyol esters are particularly preferable.

본 발명에서는 기유로서 상기 광유를 1종 사용할 수도 있고, 2종 이상을 조합하여 사용할 수도 있다. 또한, 상기 합성유를 1종 사용할 수도 있고, 2종 이상을 조합하여 사용할 수도 있다. 나아가서는, 광유 1종 이상과 합성유 1종 이상을 조합하여 사용할 수도 있다.In the present invention, one kind of the above mineral oil may be used as the base oil, or two or more kinds thereof may be used in combination. Moreover, 1 type may be used for the said synthetic oil, and may be used for it in combination of 2 or more type. Furthermore, you may use combining 1 or more types of mineral oil and 1 or more types of synthetic oils.

기유의 점도에 대해서는 특별히 제한은 없고, 윤활유 조성물의 용도에 따라 상이하지만, 통상적으로 100 ℃에서의 동점도가 바람직하게는 2 내지 30 mm2/s, 보다 바람직하게는 3 내지 15 mm2/s, 특히 바람직하게는 4 내지 10 mm2/s이다. 100 ℃에서의 동점도가 2 mm2/s 이상이면 증발 손실이 적고, 30 mm2/s 이하이면 점성 저항에 의한 동력 손실이 억제되어, 연비 개선 효과가 얻어진다.There is no restriction | limiting in particular about the viscosity of base oil, Although it changes with the use of a lubricating oil composition, Usually, the kinematic viscosity in 100 degreeC becomes like this. Preferably it is 2-30 mm <2> / s, More preferably, it is 3-15 mm <2> / s, Especially preferably, it is 4-10 mm <2> / s. If kinematic viscosity in 100 degreeC is 2 mm <2> / s or more, evaporation loss will be small, and if it is 30 mm <2> / s or less, power loss by a viscous resistance is suppressed and a fuel efficiency improvement effect will be obtained.

기유로서는, 환 분석에 의한 ％CA가 3 이하, 황 성분의 함유량이 50 질량ppm 이하인 것이 바람직하게 사용된다. 여기서, 환 분석에 의한 ％CA란, 환 분석 n-d-M법에 의해 산출한 방향족 성분의 비율(백분율)을 나타낸다. 또한, 황 성분은 JIS(일본 공업 규격, 이하 동일) K 2541에 준거하여 측정한 값이다.As base oil, what is% CA by ring analysis is 3 or less, and content of sulfur component is 50 mass ppm or less is used preferably. Here,% CA by ring analysis shows the ratio (percentage) of the aromatic component computed by the ring analysis n-d-M method. In addition, a sulfur component is the value measured based on JIS (Japanese Industrial Standards, the same below) K2541.

％CA가 3 이하, 황 성분이 50 질량ppm 이하인 기유는 양호한 산화 안정성을 나타내고, 산가의 상승이나 슬러지의 생성을 억제할 수 있음과 동시에, 금속에 대한 부식성이 적은 윤활유 조성물을 제공할 수 있다. 보다 바람직한 황 성분은 30 질량ppm 이하이다. 또한, 보다 바람직한 ％CA는 1 이하이고, 더욱 바람직하게는 0.5 이하이다.A base oil having a% CA of 3 or less and a sulfur component of 50 mass ppm or less exhibits good oxidative stability, can suppress an increase in acid value and formation of sludge, and can provide a lubricating oil composition having low corrosion resistance to metals. More preferable sulfur component is 30 mass ppm or less. Moreover, more preferable% CA is 1 or less, More preferably, it is 0.5 or less.

또한, 기유의 점도 지수는 70 이상이 바람직하고, 보다 바람직하게는 100 이상, 더욱 바람직하게는 120 이상이다. 이 점도 지수가 70 이상인 기유는, 온도의 변화에 의한 점도 변화가 작다.In addition, the viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, and still more preferably 120 or more. The base oil whose viscosity index is 70 or more has a small viscosity change by a change of temperature.

본 발명의 윤활유 조성물에는, 상기한 기유에 -C-S-C- 결합을 적어도 하나 포함하는 황 화합물이 배합되어 있다.In the lubricating oil composition of the present invention, a sulfur compound containing at least one -C-S-C- bond is blended with the base oil.

이러한 황 화합물은 윤활유 기유에 용해 또는 균일하게 분산되는 성질을 갖는 것이 바람직하고, 예를 들면 황화 유지, 황화 지방산, 황화 에스테르, 황화 올레핀, 디히드로카르빌모노술피드, 티아디아졸 화합물, 티오인산에스테르(티오포스파이트, 티오포스페이트), 알킬티오카르바모일 화합물, 티오카르바메이트 화합물, 티오테르펜 화합물, 디알킬티오디프로피오네이트 화합물 등을 들 수 있다. 이들 중에서도, 소위 황계 산화 방지제로서 사용되고 있는 황 화합물이 바람직하다.Such sulfur compounds preferably have a property of being dissolved or uniformly dispersed in lubricating oil base oils. Esters (thiophosphites, thiophosphates), alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkylthiodipropionate compounds and the like. Among these, the sulfur compound used as what is called a sulfur type antioxidant is preferable.

여기서, 황화 유지는 황이나 황 함유 화합물과 유지(라드유, 경유(whale oil), 식물유, 어유 등)를 반응시켜 얻어지는 것이며, 그의 황 함유량은 특별히 제한은 없지만, 일반적으로 5 내지 30 질량％인 것이 바람직하다. 그의 구체예로서는 황화 라드, 황화 채종유, 황화 피마자유, 황화 대두유, 황화 미강유 등을 들 수 있다. 황화 지방산의 예로서는 황화 올레산 등을, 황화 에스테르의 예로서는 황화 올레산메틸이나 황화 미강 지방산 옥틸 또는 디트리데실티오디프로피오네이트 등을 들 수 있다.Here, the sulfided fat or oil is obtained by reacting sulfur or a sulfur-containing compound with fats and oils (rad oil, whale oil, vegetable oil, fish oil, etc.), and the sulfur content thereof is not particularly limited, but is generally 5 to 30% by mass. It is preferable. Specific examples thereof include sulfurized lard, sulfided rapeseed oil, sulfided castor oil, sulfided soybean oil, sulfided rice bran oil and the like. Examples of the sulfided fatty acid include sulphide sulfide and the like, and examples of the sulfided ester include methyl oleic sulfide, sulfide rice bran fatty acid octyl or ditridecylthiodipropionate.

본 발명에서 바람직하게 사용되는 황화 올레핀으로서는, 예를 들면 하기 화학식 1로 표시되는 화합물을 들 수 있다.As a sulfide olefin used preferably by this invention, the compound represented by following formula (1) is mentioned, for example.

Figure pct00001
Figure pct00001

(식 중, R1은 탄소수 2 내지 15의 알케닐기, R2는 탄소수 2 내지 15의 알킬기 또는 알케닐기를 나타냄)(Wherein R 1 represents an alkenyl group having 2 to 15 carbon atoms, R 2 represents an alkyl group or alkenyl group having 2 to 15 carbon atoms)

이 화합물은, 탄소수 2 내지 15의 올레핀 또는 그의 이 내지 사량체를 황, 염화황 등의 황화제와 반응시킴으로써 얻어지며, 상기 올레핀으로서는 프로필렌, 이소부텐, 디이소부텐 등이 바람직하다.The compound is obtained by reacting an olefin having 2 to 15 carbon atoms or a di- tetramer thereof with a sulfiding agent such as sulfur and sulfur chloride, and as the olefin, propylene, isobutene, diisobutene and the like are preferable.

디히드로카르빌모노술피드로서는, 하기 화학식 2로 표시되는 화합물을 들 수 있다.As dihydrocarbyl monosulfide, the compound represented by following General formula (2) is mentioned.

Figure pct00002
Figure pct00002

(식 중, R3 및 R4는 각각 탄소수 1 내지 20의 알킬기 또는 환상 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기 또는 탄소수 7 내지 20의 아릴알킬기를 나타내고, 이들은 서로 동일하거나 상이할 수 있음)(Wherein R 3 and R 4 each represent an alkyl group or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and these are mutually Same or different)

여기서, R3 및 R4가 알킬기인 경우에는, 황화 알킬이라고도 불린다.Here, when R <3> and R <4> is an alkyl group, it is also called alkyl sulfide.

상기 화학식 2에서의 R3 및 R4로서는, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기, 각종 펜틸기, 각종 헥실기, 각종 헵틸기, 각종 옥틸기, 각종 노닐기, 각종 데실기, 각종 도데실기, 시클로헥실기, 시클로옥틸기, 페닐기, 나프틸기, 톨릴기, 크실릴기, 벤질기, 페네틸기 등을 들 수 있다. As R 3 and R 4 in Chemical Formula 2, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hex Practical groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, cyclohexyl groups, cyclooctyl groups, phenyl groups, naphthyl groups, tolyl groups, xylyl groups, benzyl groups, phenethyl groups, and the like. Can be.

이 디히드로카르빌모노술피드로서는, 예를 들면 디벤질모노술피드, 각종 디노닐모노술피드, 각종 디도데실모노술피드, 각종 디부틸모노술피드, 각종 디옥틸모노술피드, 디페닐모노술피드, 디시클로헥실모노술피드 등을 바람직하게 들 수 있다.Examples of the dihydrocarbyl monosulfide include dibenzyl monosulfide, various dinonyl monosulfides, various didodecyl monosulfides, various dibutyl monosulfides, various dioctyl monosulfides, and diphenyl monosulfides. Sulfide, dicyclohexyl monosulfide, etc. are mentioned preferably.

티아디아졸 화합물로서는, 예를 들면 하기 화학식 3 내지 5로 표시되는 1,3,4-티아디아졸, 1,2,4-티아디아졸 화합물, 1,4,5-티아디아졸 등이 바람직하게 사용된다.As the thiadiazole compound, for example, 1,3,4-thiadiazole, 1,2,4-thiadiazole compound, 1,4,5-thiadiazole and the like represented by the following formulas (3) to 5 are preferable. Is used.

Figure pct00003
Figure pct00003

Figure pct00004
Figure pct00004

Figure pct00005
Figure pct00005

(상기 화학식 중, R5 및 R6은 각각 독립적으로 탄소수 1 내지 20의 탄화수소기를 나타냄)(In the above formula, R 5 and R 6 each independently represent a hydrocarbon group having 1 to 20 carbon atoms)

이 티아디아졸 화합물로서는, 예를 들면 2,5-비스(n-헥실디티오)-1,3,4-티아디아졸, 2,5-비스(n-옥틸디티오)-1,3,4-티아디아졸, 2,5-비스(n-노닐디티오)-1,3,4-티아디아졸, 2,5-비스(1,1,3,3-테트라메틸부틸디티오)-1,3,4-티아디아졸, 3,5-비스(n-헥실디티오)-1,2,4-티아디아졸, 3,5-비스(n-옥틸디티오)-1,2,4-티아디아졸, 3,5-비스(n-노닐디티오)-1,2,4-티아디아졸, 3,5-비스(1,1,3,3-테트라메틸부틸디티오)-1,2,4-티아디아졸, 4,5-비스(n-헥실디티오)-1,2,3-티아디아졸, 4,5-비스(n-옥틸디티오)-1,2,3-티아디아졸, 4,5-비스(n-노닐디티오)-1,2,3-티아디아졸, 4,5-비스(1,1,3,3-테트라메틸부틸디티오)-1,2,3-티아디아졸 등을 바람직하게 들 수 있다.Examples of the thiadiazole compound include 2,5-bis (n-hexyldithio) -1,3,4-thiadiazole, 2,5-bis (n-octyldithio) -1,3, 4-thiadiazole, 2,5-bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3-tetramethylbutyldithio)- 1,3,4-thiadiazole, 3,5-bis (n-hexyldithio) -1,2,4-thiadiazole, 3,5-bis (n-octyldithio) -1,2, 4-thiadiazole, 3,5-bis (n-nonyldithio) -1,2,4-thiadiazole, 3,5-bis (1,1,3,3-tetramethylbutyldithio)- 1,2,4-thiadiazole, 4,5-bis (n-hexyldithio) -1,2,3-thiadiazole, 4,5-bis (n-octyldithio) -1,2, 3-thiadiazole, 4,5-bis (n-nonyldithio) -1,2,3-thiadiazole, 4,5-bis (1,1,3,3-tetramethylbutyldithio)- 1,2,3-thiadiazole, etc. are mentioned preferably.

티오인산에스테르로서는 알킬트리티오포스파이트, 아릴 또는 알킬아릴티오포스페이트, 디라우릴디티오인산아연 등을 들 수 있고, 특히 라우릴트리티오포스파이트, 트리페닐티오포스페이트가 바람직하다.Examples of the thiophosphate ester include alkyltrithiophosphite, aryl or alkylarylthiophosphate, dilauryldithiophosphate, and the like, and lauryltrithiophosphate and triphenylthiophosphate are particularly preferable.

알킬티오카르바모일 화합물로서는, 예를 들면 하기 화학식 6, 7을 들 수 있다.As an alkylthiocarbamoyl compound, following formula (6) and (7) are mentioned, for example.

Figure pct00006
Figure pct00006

Figure pct00007
Figure pct00007

(상기 화학식 중, R7 내지 R10은 각각 독립적으로 탄소수 1 내지 20의 알킬기를 나타내고, R11은 탄소수 1 내지 20의 알킬렌기를 나타냄)(In the above formula, R 7 to R 10 each independently represent an alkyl group having 1 to 20 carbon atoms, and R 11 represents an alkylene group having 1 to 20 carbon atoms.)

이 알킬티오카르바모일 화합물로서는, 예를 들면 비스(디메틸티오카르바모일)모노술피드, 비스(디부틸티오카르바모일)모노술피드, 비스(디메틸티오카르바모일)모노술피드, 비스(디부틸티오카르바모일)모노술피드, 비스(디아밀티오카르바모일)모노술피드, 비스(디옥틸티오카르바모일)모노술피드 및 메틸렌비스(디부틸디티오카르바메이트) 등을 바람직하게 들 수 있다.Examples of the alkylthiocarbamoyl compound include bis (dimethylthiocarbamoyl) monosulfide, bis (dibutylthiocarbamoyl) monosulfide, bis (dimethylthiocarbamoyl) monosulfide and bis (Dibutyl thiocarbamoyl) monosulfide, bis (dimylthiocarbamoyl) monosulfide, bis (dioctylthiocarbamoyl) monosulfide, methylenebis (dibutyldithiocarbamate), etc. These are mentioned preferably.

또한, 티오카르바메이트 화합물로서는, 예를 들면 디알킬디티오카르밤산아연을, 티오테르펜 화합물로서는, 예를 들면 오황화인과 피넨의 반응물을, 디알킬티오디프로피오네이트 화합물로서는, 예를 들면 디라우릴티오디프로피오네이트, 디스테아릴티오디프로피오네이트 등을 들 수 있다.As the thiocarbamate compound, for example, zinc dialkyldithiocarbamate is used. As the thioterpene compound, for example, a reactant of phosphorus penta sulfide and pinene is used as the dialkylthiodipropionate compound. Dilauryl thiodipropionate, a distearyl thiodipropionate, etc. are mentioned.

상기한 특정한 황 화합물이 윤활유 조성물 중에 존재함으로써, 엔진 부품 등의 부식을 대폭 감소시킬 수 있다.By the above-mentioned specific sulfur compound being present in the lubricating oil composition, corrosion of engine parts and the like can be greatly reduced.

단, 상기한 황 화합물의 배합량은, 화합물 중의 -C-S-C- 결합에 포함되는 황 환산량으로 조성물 전량을 기준으로 하여 0.3 질량％ 이하일 필요가 있다. -C-S-C- 결합에 포함되는 황 환산량이 0.3 질량％를 초과하면, 오히려 엔진 부품 등에 대한 부식성이 증가한다. 이 황 환산량은, 바람직하게는 0.05 내지 0.2 질량％이다.However, the compounding quantity of said sulfur compound needs to be 0.3 mass% or less in the sulfur conversion amount contained in the -C-S-C- bond in a compound based on the composition whole quantity. When the sulfur conversion amount contained in a -C-S-C- bond exceeds 0.3 mass%, the corrosiveness to engine parts etc. increases rather. This sulfur conversion amount becomes like this. Preferably it is 0.05-0.2 mass%.

또한, 황 화합물로서는, -C-Sx-C- 결합(x는 2 이상의 정수)을 포함하지 않는 것이 바람직하다. 소위 폴리술피드 구조를 갖는 황 화합물은, 엔진 부품 등에 대한 부식성의 면에서 바람직하지 않다. 특히 바이오 연료의 존재하에서는, 구리나 납의 용출량이 증가한다.Moreover, it is preferable that a sulfur compound does not contain a -CS x -C- bond (x is an integer of 2 or more). Sulfur compounds having a so-called polysulfide structure are not preferable in terms of corrosiveness to engine parts and the like. In particular, in the presence of biofuel, the elution amount of copper and lead increases.

본 발명의 윤활유 조성물에는, 알칼리 토류 금속계 청정제를 배합하는 것이 바람직하다.It is preferable to mix | blend an alkaline earth metal type detergent with the lubricating oil composition of this invention.

알칼리 토류 금속계 청정제로서는, 예를 들면 알칼리 토류 금속 술포네이트, 알칼리 토류 금속 페네이트, 알칼리 토류 금속 살리실레이트 및 이들 중에서 선택되는 2종 이상의 혼합물을 바람직하게 들 수 있다.As an alkaline earth metal type cleaning agent, alkaline earth metal sulfonate, alkaline earth metal phenate, alkaline earth metal salicylate, and 2 or more types of mixtures selected from these are mentioned, for example.

알칼리 토류 금속 술포네이트로서는 분자량 300 내지 1,500, 바람직하게는 400 내지 700의 알킬 방향족 화합물을 술폰화함으로써 얻어지는 알킬 방향족 술폰산의 알칼리 토류 금속염, 특히 마그네슘염 및/또는 칼슘염 등을 들 수 있으며, 이 중에서도 칼슘염이 바람직하게 사용된다.Alkaline earth metal sulfonates include alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 300 to 1,500, preferably 400 to 700, in particular magnesium salts and / or calcium salts. Calcium salts are preferably used.

알칼리 토류 금속 페네이트로서는, 알킬페놀, 알킬페놀술피드, 알킬페놀의 만니히 반응물의 알칼리 토류 금속염, 특히 마그네슘염 및/또는 칼슘염 등을 들 수 있으며, 이 중에서도 칼슘염이 특히 바람직하게 사용된다.Examples of the alkaline earth metal phenate include alkali earth metal salts, especially magnesium salts and / or calcium salts of alkylphenols, alkylphenol sulfides, and Mannich reactants of alkylphenols, and calcium salts are particularly preferably used. .

알칼리 토류 금속 살리실레이트로서는 알킬살리실산의 알칼리 토류 금속염, 특히 마그네슘염 및/또는 칼슘염 등을 들 수 있으며, 이 중에서도 칼슘염이 바람직하게 사용된다. 상기 알칼리 토류 금속계 청정제를 구성하는 알킬기로서는 탄소수 4 내지 30인 것이 바람직하고, 보다 바람직하게는 6 내지 18의 직쇄 또는 분지 알킬기이고, 이들은 직쇄일 수도 있고, 분지일 수도 있다. 또한, 이들은 1급 알킬기, 2급 알킬기 또는 3급 알킬기일 수도 있다.Examples of the alkaline earth metal salicylate include alkaline earth metal salts of alkyl salicylic acid, in particular magnesium salts and / or calcium salts. Among these, calcium salts are preferably used. As an alkyl group which comprises the said alkaline-earth metal type detergent, it is preferable that it is C4-C30, More preferably, it is a 6-18 chain or branched alkyl group, These may be linear or branched. In addition, these may be primary alkyl groups, secondary alkyl groups, or tertiary alkyl groups.

또한, 알칼리 토류 금속 술포네이트, 알칼리 토류 금속 페네이트 및 알칼리 토류 금속 살리실레이트로서는, 상기 알킬 방향족 술폰산, 알킬페놀, 알킬페놀술피드, 알킬페놀의 만니히 반응물, 알킬살리실산 등을 직접 마그네슘 및/또는 칼슘의 알칼리 토류 금속의 산화물이나 수산화물 등의 알칼리 토류 금속 염기와 반응시키거나, 또는 1회 나트륨염이나 칼륨염 등의 알칼리 금속염으로 한 후, 알칼리 토류 금속염으로 치환시킴으로써 얻어지는 중성 알칼리 토류 금속 술포네이트, 중성 알칼리 토류 금속 페네이트 및 중성 알칼리 토류 금속 살리실레이트뿐만 아니라, 중성 알칼리 토류 금속 술포네이트, 중성 알칼리 토류 금속 페네이트 및 중성 알칼리 토류 금속 살리실레이트와 과잉의 알칼리 토류 금속염이나 알칼리 토류 금속 염기를 물의 존재하에 가열함으로써 얻어지는 염기성 알칼리 토류 금속 술포네이트, 염기성 알칼리 토류 금속 페네이트 및 염기성 알칼리 토류 금속 살리실레이트나, 탄산 가스의 존재하에 중성 알칼리 토류 금속 술포네이트, 중성 알칼리 토류 금속 페네이트 및 중성 알칼리 토류 금속 살리실레이트를 알칼리 토류 금속의 탄산염 또는 붕산염을 반응시킴으로써 얻어지는 과염기성 알칼리 토류 금속 술포네이트, 과염기성 알칼리 토류 금속 페네이트 및 과염기성 알칼리 토류 금속 살리실레이트도 포함된다.In addition, as alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate, the said alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, the Mannich reactant of alkylphenol, alkyl salicylic acid, etc. can be directly magnesium and //. Or a neutral alkaline earth metal sulfonate obtained by reacting with an alkaline earth metal base such as an oxide or hydroxide of an alkaline earth metal of calcium, or an alkali metal salt such as sodium salt or potassium salt and then substituting with an alkaline earth metal salt. Excessive alkaline earth metal salts or alkaline earth metal bases with neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates, as well as neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates In the presence of water Basic alkaline earth metal sulfonates, basic alkaline earth metal phenates and basic alkaline earth metal salicylates obtained by Also included are overbased alkaline earth metal sulfonates, overbased alkaline earth metal phenates and overbased alkaline earth metal salicylates obtained by reacting a rate with a carbonate or borate salt of an alkaline earth metal.

본 발명에서 알칼리 토류 금속계 청정제의 배합량은 알칼리 토류 금속 환산량으로 0.35 질량％ 이하이고, 바람직하게는 0.01 내지 0.35 질량％이고, 보다 바람직하게는 0.1 내지 0.35 질량％이다. 알칼리 토류 금속계 청정제의 배합량이 0.01 질량％ 이상이면, 산화 안정성, 염기가 유지성 및 고온 청정성이 보다 우수한 윤활유 조성물이 된다. 한편, 알칼리 토류 금속계 청정제의 배합량이 0.35 질량％를 초과하면, 배출 가스를 정화하는 촉매의 성능 저하를 야기할 우려가 있다. 또한, DPF 장착 디젤 엔진에 적용한 경우, DPF로의 회분 부착량이 많아져 DPF의 수명을 짧게 할 우려가 있다.In this invention, the compounding quantity of alkaline-earth metal type detergent is 0.35 mass% or less in conversion of alkaline earth metals, Preferably it is 0.01-0.35 mass%, More preferably, it is 0.1-0.35 mass%. When the compounding quantity of the alkaline earth metal-based cleaning agent is 0.01% by mass or more, a lubricating oil composition having more excellent oxidation stability, base oil retention, and high temperature cleanability is obtained. On the other hand, when the compounding quantity of alkaline-earth metal type cleaning agent exceeds 0.35 mass%, there exists a possibility of causing the performance fall of the catalyst which purifies exhaust gas. In addition, when applied to a diesel engine equipped with a DPF, there is a fear that the ash adhesion amount to the DPF increases, thereby shortening the life of the DPF.

본 발명의 윤활유 조성물에는, 산화 방지제로서 페놀계 산화 방지제 및/또는 아민계 산화 방지제를 배합하는 것이 바람직하다.It is preferable to mix | blend a phenolic antioxidant and / or an amine antioxidant to the lubricating oil composition of this invention as antioxidant.

페놀계 산화 방지제로서는, 예를 들면 옥타데실-3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트, 4,4'-메틸렌비스(2,6-디-t-부틸페놀); 4,4'-비스(2,6-디-t-부틸페놀); 4,4'-비스(2-메틸-6-t-부틸페놀); 2,2'-메틸렌비스(4-에틸-6-t-부틸페놀); 2,2'-메틸렌비스(4-메틸-6-t-부틸페놀); 4,4'-부틸리덴비스(3-메틸-6-t-부틸페놀); 4,4'-이소프로필리덴비스(2,6-디-t-부틸페놀); 2,2'-메틸렌비스(4-메틸-6-노닐페놀); 2,2'-이소부틸리덴비스(4,6-디메틸페놀); 2,2'-메틸렌비스(4-메틸-6-시클로헥실페놀); 2,6-디-t-부틸-4-메틸페놀; 2,6-디-t-부틸-4-에틸페놀; 2,4-디메틸-6-t-부틸페놀; 2,6-디-t-아밀-p-크레졸; 2,6-디-t-부틸-4-(N,N'-디메틸아미노메틸페놀); 4,4'-티오비스(2-메틸-6-t-부틸페놀); 4,4'-티오비스(3-메틸-6-t-부틸페놀); 2,2'-티오비스(4-메틸-6-t-부틸페놀); 비스(3-메틸-4-히드록시-5-t-부틸벤질)술피드; 비스(3,5-디-t-부틸-4-히드록시벤질)술피드; n-옥틸-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트, n-옥타데실-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트; 2,2'-티오[디에틸-비스-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 등을 들 수 있다. 이들 중에서, 특히 비스페놀계 및 에스테르기 함유 페놀계인 것이 바람직하다.As a phenolic antioxidant, octadecyl-3- (3,5-di-tert- butyl- 4-hydroxyphenyl) propionate, 4,4'- methylenebis (2, 6- di-t, for example) Butylphenol); 4,4'-bis (2,6-di-t-butylphenol); 4,4'-bis (2-methyl-6-t-butylphenol); 2,2'-methylenebis (4-ethyl-6-t-butylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 4,4'-butylidenebis (3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis (2,6-di-t-butylphenol); 2,2'-methylenebis (4-methyl-6-nonylphenol); 2,2'-isobutylidenebis (4,6-dimethylphenol); 2,2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethylphenol; 2,4-dimethyl-6-t-butylphenol; 2,6-di-t-amyl-p-cresol; 2,6-di-t-butyl-4- (N, N'-dimethylaminomethylphenol); 4,4'-thiobis (2-methyl-6-t-butylphenol); 4,4'-thiobis (3-methyl-6-t-butylphenol); 2,2'-thiobis (4-methyl-6-t-butylphenol); Bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide; Bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide; n-octyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl Propionate; 2,2'-thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] etc. are mentioned. Among these, it is especially preferable that they are bisphenol type and ester group containing phenol type.

또한, 아민계 산화 방지제로서는, 예를 들면 모노옥틸디페닐아민; 모노노닐디페닐아민 등의 모노알킬디페닐아민계, 4,4'-디부틸디페닐아민; 4,4'-디펜틸디페닐아민; 4,4'-디헥실디페닐아민; 4,4'-디헵틸디페닐아민; 4,4'-디옥틸디페닐아민; 4,4'-디노닐디페닐아민 등의 디알킬디페닐아민계, 테트라부틸디페닐아민; 테트라헥실디페닐아민; 테트라옥틸디페닐아민; 테트라노닐디페닐아민 등의 폴리알킬디페닐아민계 및 나프틸아민계인 것, 구체적으로는 α-나프틸아민; 페닐-α-나프틸아민; 나아가서는 부틸페닐-α-나프틸아민; 펜틸페닐-α-나프틸아민; 헥실페닐-α-나프틸아민; 헵틸페닐-α-나프틸아민; 옥틸페닐-α-나프틸아민; 노닐페닐-α-나프틸아민 등의 알킬 치환 페닐-α-나프틸아민 등을 들 수 있다. 이들 중에서 디알킬디페닐아민계 및 나프틸아민계인 것이 바람직하다.Moreover, as an amine antioxidant, For example, monooctyl diphenylamine; Monoalkyl diphenylamines such as monononyldiphenylamine, 4,4'-dibutyldiphenylamine; 4,4'-dipentyldiphenylamine; 4,4'-dihexyldiphenylamine; 4,4'-diheptyldiphenylamine; 4,4'-dioctyldiphenylamine; Dialkyl diphenylamines such as 4,4'-dinonyldiphenylamine and tetrabutyldiphenylamine; Tetrahexyldiphenylamine; Tetraoctyldiphenylamine; Polyalkyldiphenylamine and naphthylamine such as tetranonyldiphenylamine, and specifically, α-naphthylamine; Phenyl-α-naphthylamine; Further butylphenyl-α-naphthylamine; Pentylphenyl-α-naphthylamine; Hexylphenyl-α-naphthylamine; Heptylphenyl-α-naphthylamine; Octylphenyl-α-naphthylamine; Alkyl-substituted phenyl-alpha-naphthylamine, such as nonylphenyl alpha-naphthylamine, etc. are mentioned. It is preferable that they are dialkyl diphenylamine type and naphthylamine type among these.

또한, 다른 산화 방지제로서, 몰리브덴 아민 착체계 산화 방지제를 사용할 수도 있다. 몰리브덴 아민 착체계 산화 방지제로서는, 6가의 몰리브덴 화합물, 구체적으로는 3산화몰리브덴 및/또는 몰리브덴산과 아민 화합물을 반응시켜 이루어지는 것, 예를 들면 일본 특허 공개 제2003-252887호 공보에 기재된 제조 방법으로 얻어지는 화합물을 사용할 수 있다. 6가의 몰리브덴 화합물과 반응시키는 아민 화합물로서는 특별히 제한되지 않지만, 구체적으로는 모노아민, 디아민, 폴리아민 및 알칸올아민을 들 수 있다. 보다 구체적으로는 메틸아민, 에틸아민, 디메틸아민, 디에틸아민, 메틸에틸아민, 메틸프로필아민 등의 탄소수 1 내지 30의 알킬기(이들 알킬기는 직쇄상일 수도 있고, 분지상일 수도 있음)를 갖는 알킬아민; 에테닐아민, 프로페닐아민, 부테닐아민, 옥테닐아민 및 올레일아민 등의 탄소수 2 내지 30의 알케닐기(이들 알케닐기는 직쇄상일 수도 있고, 분지상일 수도 있음)를 갖는 알케닐아민; 메탄올아민, 에탄올아민, 메탄올에탄올아민, 메탄올프로판올아민 등의 탄소수 1 내지 30의 알칸올기(이들 알칸올기는 직쇄상일 수도 있고, 분지상일 수도 있음)를 갖는 알칸올아민; 메틸렌디아민, 에틸렌디아민, 프로필렌디아민 및 부틸렌디아민 등의 탄소수 1 내지 30의 알킬렌기를 갖는 알킬렌디아민; 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민, 펜타에틸렌헥사민 등의 폴리아민; 운데실디에틸아민, 운데실디에탄올아민, 도데실디프로판올아민, 올레일디에탄올아민, 올레일프로필렌디아민, 스테아릴테트라에틸렌펜타민 등의 상기 모노아민, 디아민, 폴리아민에 탄소수 8 내지 20의 알킬기 또는 알케닐기를 갖는 화합물이나 이미다졸린 등의 복소환 화합물; 이들 화합물의 알킬렌옥시드 부가물; 및 이들의 혼합물 등을 예시할 수 있다. 또한, 일본 특허 공고 (평)3-22438호 공보 및 일본 특허 공개 제2004-2866호 공보에 기재되어 있는 숙신산이미드의 황 함유 몰리브덴 착체 등을 예시할 수 있다.Moreover, as another antioxidant, the molybdenum amine complex system antioxidant can also be used. As the molybdenum amine complex antioxidant, a hexavalent molybdenum compound, specifically, a compound obtained by reacting molybdenum trioxide and / or molybdate acid with an amine compound, for example, obtained by the production method described in JP-A-2003-252887 Compounds can be used. Although it does not restrict | limit especially as an amine compound made to react with a hexavalent molybdenum compound, Specifically, a monoamine, a diamine, a polyamine, and an alkanolamine are mentioned. More specifically, alkyl having an alkyl group having 1 to 30 carbon atoms (the alkyl group may be linear or branched) such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine and methylpropylamine. Amines; Alkenylamines having alkenyl groups having 2 to 30 carbon atoms (the alkenyl groups may be linear or branched) such as ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine; Alkanolamines having an alkanol group having 1 to 30 carbon atoms (these alkanol groups may be linear or branched) such as methanol amine, ethanol amine, methanol ethanol amine and methanol propanol amine; Alkylenediamines having an alkylene group having 1 to 30 carbon atoms such as methylenediamine, ethylenediamine, propylenediamine and butylenediamine; Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; An alkyl group having 8 to 20 carbon atoms or alkenyl to the above monoamines, diamines, and polyamines, such as undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine, oleyl diethanolamine, oleylpropylenediamine, and stearyltetraethylenepentamine Heterocyclic compounds such as a compound having a group and imidazoline; Alkylene oxide adducts of these compounds; And mixtures thereof. Moreover, the sulfur containing molybdenum complex of the succinimide described in Unexamined-Japanese-Patent No. 3-22438 and Unexamined-Japanese-Patent No. 2004-2866 can be illustrated.

상술한 산화 방지제의 배합량은, 조성물 전량 기준으로, 0.3 질량％ 이상이고, 바람직하게는 0.5 질량％ 이상이다. 한편, 2 질량％를 초과하면, 윤활유 기유에 불용이 될 우려가 있다. 따라서, 산화 방지제의 배합량은, 조성물 전량 기준으로 0.3 내지 2 질량％의 범위가 바람직하다.The compounding quantity of the above-mentioned antioxidant is 0.3 mass% or more on the basis of a composition whole quantity, Preferably it is 0.5 mass% or more. On the other hand, when it exceeds 2 mass%, there is a possibility that it becomes insoluble in lubricating oil base oil. Therefore, the compounding quantity of antioxidant has the preferable range of 0.3-2 mass% on the basis of a composition whole quantity.

본 발명의 윤활유 조성물에는, 본 발명의 효과를 손상시키지 않는 범위에서 필요에 따라 다른 첨가제, 예를 들면 점도 지수 향상제, 유동점 강하제, 내마모제, 무회계 마찰 감소제, 방청제, 금속 불활성화제, 계면활성제 및 소포제 등을 배합할 수도 있다.In the lubricating oil composition of the present invention, other additives, such as viscosity index improvers, pour point depressants, antiwear agents, ashless friction reducers, rust inhibitors, metal deactivators, surfactants, and antifoaming agents, as necessary, within a range that does not impair the effects of the present invention. Etc. can also be mix | blended.

점도 지수 향상제로서는, 예를 들면 폴리메타크릴레이트, 분산형 폴리메타크릴레이트, 올레핀계 공중합체(예를 들면, 에틸렌-프로필렌 공중합체 등), 분산형 올레핀계 공중합체, 스티렌계 공중합체(예를 들면, 스티렌-디엔 공중합체, 스티렌-이소프렌 공중합체 등) 등을 들 수 있다. 이들 점도 지수 향상제의 배합량은 배합 효과의 면에서, 조성물 전량 기준으로 0.5 내지 15 질량％ 정도이고, 바람직하게는 1 내지 10 질량％이다.Examples of the viscosity index improver include polymethacrylates, dispersed polymethacrylates, olefin copolymers (for example, ethylene-propylene copolymers, etc.), dispersed olefin copolymers, and styrene copolymers (examples). For example, a styrene diene copolymer, a styrene isoprene copolymer, etc. can be mentioned. The compounding quantity of these viscosity index improvers is about 0.5-15 mass% in terms of a composition whole quantity, Preferably it is 1-10 mass% from a viewpoint of a compounding effect.

유동점 강하제로서는, 예를 들면 질량 평균 분자량이 5000 내지 50,000 정도인 폴리메타크릴레이트 등을 들 수 있다.As a pour point lowering agent, the polymethacrylate etc. which have a mass mean molecular weight about 5000-50,000 are mentioned, for example.

내마모제로서는, 디티오인산아연, 디티오카르밤산아연, 인산아연, 디술피드류, 황화 올레핀류, 황화 유지류, 황화 에스테르류, 티오카르보네이트류, 티오카르바메이트류(예를 들면, Mo-DTC) 등의 황 함유 화합물; 아인산에스테르류, 인산에스테르류, 포스폰산에스테르류 및 이들의 아민염 또는 금속염 등의 인 함유 화합물; 티오아인산에스테르류, 티오인산에스테르류(예를 들면, Mo-DTP), 티오포스폰산에스테르류 및 이들의 아민염 또는 금속염 등의 황 및 인 함유 마모 방지제를 들 수 있다. 단, 이들은 엔진 부품 등에 대한 부식성을 증가시킬 우려도 있기 때문에, 본 발명에서의 상기 황 화합물과의 병용에는 유의할 필요가 있다.Examples of the antiwear agent include zinc dithiophosphate, zinc dithiocarbamate, zinc phosphate, disulfides, sulfided olefins, sulfurized fats and oils, sulfided esters, thiocarbonates, and thiocarbamates (e.g., Mo- Sulfur-containing compounds such as DTC); Phosphorus-containing compounds such as phosphite esters, phosphate esters, phosphonic acid esters, and amine salts and metal salts thereof; Sulfur and phosphorus containing antiwear agents, such as thiophosphoric acid ester, thiophosphoric acid ester (for example, Mo-DTP), thiophosphonic acid ester, these amine salt, or a metal salt, are mentioned. However, since these may increase the corrosiveness to engine parts and the like, it is necessary to pay attention to the combination with the sulfur compound in the present invention.

무회계 마찰 감소제로서는, 예를 들면 모노 타입 또는 비스 타입의 폴리부테닐숙신산이미드 및/또는 그의 붕소화물, 벤질아민, 폴리알케닐아민 등을 들 수 있으며, 질량 평균 분자량이 700 내지 3500인 폴리부테닐기를 갖는 폴리부테닐숙신산이미드가 바람직하다. 그 이외에, 예를 들면 탄소수 6 내지 30의 알킬기 또는 알케닐기를 분자 중에 적어도 1개 갖는 지방산, 지방족 알코올, 지방족 에테르, 지방족 에스테르, 지방족 아민 및 지방족 아미드 등도 들 수 있다.As the ashless friction reducing agent, for example, polybutenyl succinimide of mono type or bis type and / or its boride, benzylamine, polyalkenylamine and the like can be mentioned. Polybutenyl succinimides having a butenyl group are preferred. In addition, for example, there may be mentioned fatty acids, aliphatic alcohols, aliphatic ethers, aliphatic esters, aliphatic amines and aliphatic amides having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms in the molecule.

무회계 분산제로서는, 무회계 분산제의 함유 비율은 기유 100 질량부에 대하여 0.5 내지 10 질량부가 바람직하다.As the ashless dispersant, the content ratio of the ashless dispersant is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the base oil.

방청제로서는, 석유 술포네이트, 알킬벤젠술포네이트, 디노닐나프탈렌술포네이트, 알케닐숙신산에스테르, 다가 알코올 에스테르 등을 들 수 있다. 이들 방청제의 배합량은 배합 효과의 면에서, 조성물 전량 기준으로 통상적으로 0.01 내지 1 질량％ 정도이고, 바람직하게는 0.05 내지 0.5 질량％이다.Petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinic acid ester, polyhydric alcohol ester, etc. are mentioned as a rust inhibitor. The compounding quantity of these rust inhibitors is about 0.01-1 mass% normally on the basis of composition whole quantity from the viewpoint of a compounding effect, Preferably it is 0.05-0.5 mass%.

금속 불활성화제(구리 부식 방지제)로서는, 예를 들면 벤조트리아졸계, 톨릴트리아졸계, 티아디아졸계, 이미다졸계 및 피리미딘계 화합물 등을 들 수 있다. 이 중에서 벤조트리아졸계 화합물이 바람직하다. 금속 불활성화제를 배합함으로써 엔진 부품의 금속 부식 및 산화 열화를 억제할 수 있다. 이러한 금속 불활성화제는, 상기한 소정의 황 화합물과 병용하는 것이 바람직하다.As a metal deactivator (copper corrosion inhibitor), a benzotriazole type, a tolyl triazole type, a thiadiazole type, an imidazole type, a pyrimidine type compound, etc. are mentioned, for example. Among these, benzotriazole type compounds are preferable. By incorporating a metal deactivator, metal corrosion and oxidative degradation of engine parts can be suppressed. It is preferable to use such a metal deactivator together with said predetermined sulfur compound.

이들 금속 불활성화제의 배합량은 배합 효과의 면에서, 조성물 전량 기준으로 바람직하게는 0.01 내지 0.1 질량％, 보다 바람직하게는 0.03 내지 0.05 질량％이다.The amount of these metal deactivators is preferably 0.01 to 0.1 mass%, more preferably 0.03 to 0.05 mass%, based on the total amount of the composition, in view of the blending effect.

계면활성제로서는, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌알킬페닐에테르 및 폴리옥시에틸렌알킬나프틸에테르 등의 폴리알킬렌글리콜계 비이온성 계면활성제 등을 들 수 있다.As surfactant, polyalkylene glycol type | system | group nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether, etc. are mentioned.

소포제로서는, 실리콘유, 플루오로 실리콘유 및 플루오로알킬에테르 등을 들 수 있으며, 소포 효과 및 경제성의 균형 등의 면에서 조성물 전량에 기초하여 0.005 내지 0.1 질량％ 정도 배합하는 것이 바람직하다.Examples of the antifoaming agent include silicone oil, fluorosilicone oil, fluoroalkyl ether, and the like, and are preferably blended in an amount of 0.005 to 0.1% by mass based on the total amount of the composition in view of the balance between the defoaming effect and economical efficiency.

본 발명의 윤활유 조성물에서는, 황 함유량이 조성물 전량 기준으로 0.5 질량％ 이하인 것이 바람직하고, 0.3 질량％ 이하인 것이 보다 바람직하고, 더욱 바람직하게는 0.2 질량％ 이하이다. 황 함유량이 0.5 질량％ 이하이면, 배출 가스를 정화하는 촉매의 성능 저하를 효과적으로 억제할 수 있다.In the lubricating oil composition of this invention, it is preferable that sulfur content is 0.5 mass% or less on the basis of a composition whole quantity, It is more preferable that it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less. If sulfur content is 0.5 mass% or less, the performance fall of the catalyst which purifies exhaust gas can be suppressed effectively.

본 발명의 윤활유 조성물에서는, 인 함유량이 조성물 전량 기준으로 0.12 질량％ 이하인 것이 바람직하고, 보다 바람직하게는 0.1 질량％ 이하이다. 인 함유량이 0.12 질량％ 이하이면, 배출 가스를 정화하는 촉매의 성능 저하를 효과적으로 억제할 수 있다.In the lubricating oil composition of this invention, it is preferable that phosphorus content is 0.12 mass% or less on the basis of a composition whole quantity, More preferably, it is 0.1 mass% or less. When phosphorus content is 0.12 mass% or less, the performance fall of the catalyst which purifies exhaust gas can be suppressed effectively.

또한, 본 발명의 윤활유 조성물에서는 황산 회분이 1.1 질량％ 이하인 것이 바람직하고, 1 질량％ 이하인 것이 보다 바람직하다. 황산 회분이 1.1 질량％ 이하이면, 배출 가스를 정화하는 촉매의 성능 저하를 효과적으로 억제할 수 있다. 또한, 디젤 엔진에서는 DPF의 필터에 퇴적되는 회분량이 적어, 상기 필터의 회분 클로깅이 억제되고 DPF의 수명이 길어진다. 또한, 이 황산 회분이란, 시료를 태워서 발생한 탄화 잔류물에 황산을 첨가하여 가열하여 항량(constant mass)으로 한 회분을 말하며, 통상적으로 윤활유 조성물 중의 금속계 첨가제의 대략적인 양을 알기 위해 사용된다. 구체적으로는, JIS K 2272의 "5. 황산 회분 시험 방법"에 규정되어 있는 방법에 의해 측정된다.Moreover, in the lubricating oil composition of this invention, it is preferable that sulfuric acid ash is 1.1 mass% or less, and it is more preferable that it is 1 mass% or less. When sulfuric acid ash is 1.1 mass% or less, the performance fall of the catalyst which purifies exhaust gas can be suppressed effectively. In addition, in a diesel engine, the amount of ash deposited on the filter of the DPF is small, the ash clogging of the filter is suppressed, and the life of the DPF is long. In addition, this sulfuric acid ash content means ash content which is made by adding sulfuric acid to the carbonization residue which burned the sample, and heated it as a constant mass, and is normally used in order to know the approximate amount of the metallic additive in a lubricating oil composition. Specifically, it measures by the method prescribed | regulated to "5. Sulfuric acid ash test method" of JISK2272.

또한, 내연 기관에서 윤활유 증발성의 증대는 윤활유 자체의 소비량 증가를 초래하고, 그에 따른 윤활유 수명의 저하, 나아가서는 배기 가스 촉매로의 비산량 증대에 의한 촉매 능력ㆍ수명의 저하를 야기한다. 이러한 관점으로부터 본 발명의 윤활유 조성물에서는, JPI(일본 석유 학회, 이하 동일)-5S-41-93에 준거하여 측정되는 노악(NOACK) 증발량이 15 질량％ 이하인 것이 바람직하고, 보다 바람직하게는 13 질량％ 이하이고, 더욱 바람직하게는 10 질량％ 이하이다.In addition, an increase in lubricating oil evaporation in an internal combustion engine leads to an increase in consumption of lubricating oil itself, and thus a decrease in lubricating oil life, and thus a decrease in catalyst capacity and lifetime by increasing scattering amount to an exhaust gas catalyst. From this point of view, in the lubricating oil composition of the present invention, the amount of NOACK evaporation measured based on JPI (Japanese Petroleum Institute, hereinafter same) -5S-41-93 is preferably 15% by mass or less, more preferably 13% by mass. It is% or less, More preferably, it is 10 mass% or less.

[실시예][Example]

이어서, 본 발명을 실시예에 의해 더욱 상세히 설명하지만, 본 발명은 이들 예에 의해 한정되지 않는다.Next, although an Example demonstrates this invention still in detail, this invention is not limited by these examples.

〔실시예 1 내지 2, 비교예 1 내지 4〕[Examples 1 to 2 and Comparative Examples 1 to 4]

표 1에 나타낸 배합 조성을 갖는 윤활유 조성물을 제조하여, 이하에 나타내는 부식성 시험을 행하였다. 또한, 윤활유 조성물의 제조에 사용한 각 성분의 종류는 다음과 같다.The lubricating oil composition which has the compounding composition shown in Table 1 was manufactured, and the corrosion test shown below was done. In addition, the kind of each component used for manufacture of a lubricating oil composition is as follows.

(1) 기유: 수소화 정제 기유, 40 ℃ 동점도 20.4 mm2/s, 100 ℃ 동점도 4.28 mm2/s, 점도 지수 116, ％CA 0.0, 황 함유량 20 질량ppm 미만(1) Base oil: hydrogenated refining base oil, 40 ℃ kinematic viscosity 20.4 mm 2 / s, 100 ℃ kinematic viscosity 4.28 mm 2 / s, viscosity index of 116,% CA 0.0, a sulfur content less than 20 ppm by weight

(2) 점도 지수 향상제: OCP, 질량 평균 분자량 800,000(2) Viscosity index improver: OCP, mass average molecular weight 800,000

(3) 유동점 강하제: 폴리알킬메타크릴레이트, 질량 평균 분자량 60,000(3) Pour point depressant: Polyalkyl methacrylate, mass average molecular weight 60,000

(4) 금속계 청정제: 과염기성 칼슘 살리실레이트, 염기가(과염소산법) 225 mgKOH/g, 칼슘 함유량 7.8 질량％, 황 함유량 0.3 질량％(4) Metallic detergent: overbased calcium salicylate, base value (perchloric acid method) 225 mgKOH / g, calcium content 7.8 mass%, sulfur content 0.3 mass%

(5) 폴리부테닐숙신산모노이미드 A: 폴리부테닐기의 수 평균 분자량 1000, 질소 함유량 1.2 질량％, 붕소 함유량 1.3 질량％(5) Polybutenyl succinate monoimide A: number average molecular weight 1000 of polybutenyl group, 1.2 mass% of nitrogen content, 1.3 mass% of boron content

(6) 폴리부테닐숙신산비스이미드 B: 폴리부테닐기의 수 평균 분자량 2,000, 질소 함유량 1.2 질량％(6) Polybutenyl succinic acid bisimide B: Number average molecular weight 2,000 of polybutenyl group, 1.2 mass% of nitrogen content

(7) 페놀계 산화 방지제: 옥타데실 3-(3,5-tert-부틸-4-히드록시페닐)프로피오네이트(7) Phenolic antioxidant: Octadecyl 3- (3,5-tert-butyl-4-hydroxyphenyl) propionate

(8) 아민계 산화 방지제: 디알킬디페닐아민, 질소 함유량 4.62 질량％(8) Amine antioxidant: dialkyldiphenylamine, nitrogen content 4.62 mass%

(9) 디알킬디티오인산아연: Zn 함유량 9.0 질량％, 인 함유량 8.2 질량％, 황 함유량 17.1 질량％, 알킬기; 제2급 부틸기와 제2급 헥실기의 혼합물(9) dialkyldithiophosphate: Zn content 9.0 mass%, phosphorus content 8.2 mass%, sulfur content 17.1 mass%, an alkyl group; Mixture of secondary butyl and secondary hexyl groups

(10) 황계 산화 방지제 A: 메틸렌비스(디부틸디티오카르바메이트)(10) sulfur-based antioxidant A: methylenebis (dibutyldithiocarbamate)

(11) 황계 산화 방지제 B: 디트리데실티오디프로피오네이트(11) Sulfur type antioxidant B: Ditridecyl thiodipropionate

(12) 황계 산화 방지제 C: 디-t-도데실트리술피드(12) sulfur-based antioxidant C: di-t-dodecyltrisulfide

(13) 황계 산화 방지제 D: MoDTC(13) sulfur-based antioxidant D: MoDTC

(14) 구리 부식 방지제: 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸(14) Copper corrosion inhibitor: 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole

(15) 소포제: 실리콘계 소포제(15) Defoamer: Silicone antifoam

각 윤활유 조성물의 성상 측정 및 부식성 시험에 대해서는, 이하와 같이 하여 행하였다.The property measurement and the corrosiveness test of each lubricating oil composition were performed as follows.

(칼슘 함유량)(Calcium content)

JPI-5S-38-92에 준거하여 측정하였다.It measured based on JPI-5S-38-92.

(황 함유량)(Sulfur content)

JIS K 2541에 준거하여 측정하였다.It measured according to JISK2541.

(인 함유량)(Phosphorus content)

JPI-5S-38-92에 준거하여 측정하였다.It measured based on JPI-5S-38-92.

(황산 회분)(Sulfuric acid ash)

JIS K 2272에 준거하여 측정하였다.It measured based on JISK2272.

(부식성 시험)Corrosion Test

시험용의 윤활유 조성물로서는, 내연 기관 내에서의 연료와 윤활유의 혼합 비율을 상정하여, 상기한 각 윤활유 조성물(신유, new oil)에 대하여 바이오 연료(채종유를 메틸 알코올에 의해 에스테르 교환하여 얻어진 연료)를 10 질량％ 배합한 혼합유를 사용하였다.As the lubricating oil composition for the test, a mixture ratio of fuel and lubricating oil in the internal combustion engine is assumed, and biofuel (fuel obtained by transesterifying rapeseed oil with methyl alcohol) is used for each of the lubricating oil compositions (new oil, new oil) described above. 10 mass% blended oil was used.

부식성 시험은, 시료로서 각 100 g의 혼합유를 유리 용기(직경 40 mm×높이 300 mm)에 충전한 후, 오일 온도를 125 ℃로 유지하면서 공기를 88 ml/분의 조건으로 168 시간 동안 취입하였다. 그 후, 시료유 중에 용출된 구리(Cu)와 납(Pb)의 양을 플라즈마 발광 분광 분석(ICP)으로 측정하였다.In the corrosive test, each 100 g of mixed oil was filled as a sample into a glass container (40 mm in diameter x 300 mm in height), followed by blowing air at 88 ml / min for 168 hours while maintaining the oil temperature at 125 ° C. It was. Thereafter, the amounts of copper (Cu) and lead (Pb) eluted in the sample oil were measured by plasma emission spectroscopy (ICP).

또한, 참고예로서, 바이오 연료를 혼합하지 않는 윤활유 조성물에 대해서도 동일하게 부식성 시험을 행하였다.In addition, as a reference example, the corrosion test was similarly performed also about the lubricating oil composition which does not mix a biofuel.

각 윤활유 조성물의 성상 및 부식성 시험의 결과를 표 1에 나타낸다.Table 1 shows the properties of the lubricating oil compositions and the results of the corrosion test.

Figure pct00008
Figure pct00008

〔평가 결과〕〔Evaluation results〕

표 1의 부식성 시험 결과로부터 알 수 있는 바와 같이, 본 발명의 윤활유 조성물을 사용한 실시예 1 내지 2에서는, 바이오 연료를 첨가한 윤활유 조성물에 적용하여도 구리(Cu)와 납(Pb)의 용출량은 근소하였다. 특히, 참고예 1, 2와 같이 바이오 연료를 첨가하지 않은 계에 비해서도 납의 용출량이 적다는 것은 특필할 만한 점이다.As can be seen from the results of the corrosive test of Table 1, in Examples 1 to 2 using the lubricating oil composition of the present invention, even when applied to the lubricating oil composition to which biofuel was added, the elution amounts of copper (Cu) and lead (Pb) were It was small. In particular, it is worth noting that the amount of elution of lead is smaller than that of the system without adding the biofuel as in Reference Examples 1 and 2.

한편, 비교예 1과 같이 본 발명에서의 특정한 황 화합물이 배합되어 있지 않으면, 구리나 납의 용출량이 많아진다. 또한, 황 화합물이 배합되어 있어도, 비교예 2, 3과 같이 폴리술피드 등이면 구리나 납의 용출량은 오히려 증가한다.On the other hand, when the specific sulfur compound in this invention is not mix | blended like the comparative example 1, the elution amount of copper and lead will increase. Moreover, even if the sulfur compound is mix | blended, if it is polysulfide etc. like the comparative examples 2 and 3, the elution amount of copper and lead will rather increase.

또한, 본 발명에서의 특정한 황 화합물이 배합되어 있어도, 비교예 4와 같이 그의 양이 지나치게 많으면 구리의 용출량이 증가한다.Moreover, even if the specific sulfur compound in this invention is mix | blended, when the quantity is too large like Comparative Example 4, the amount of copper eluted increases.

본 발명의 윤활유 조성물은 바이오 연료 또는 바이오 연료를 포함하는 연료를 사용하는 내연 기관에 바람직하게 이용할 수 있다.The lubricating oil composition of the present invention can be preferably used for an internal combustion engine using a biofuel or a fuel containing a biofuel.

Claims (7)

천연 유지, 천연 유지의 수소화 처리물, 천연 유지의 에스테르 교환물 및 천연 유지의 에스테르 교환물의 수소화 처리물 중으로부터 선택된 적어도 1종을 포함하는 연료를 사용하는 내연 기관에서 사용되는 윤활유 조성물이며,
기유에 -C-S-C- 결합을 적어도 하나 포함하는 황 화합물이 배합되고,
상기 -C-S-C- 결합에 포함되는 황이 조성물 전량 기준으로 0.3 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.It is a lubricating oil composition used in an internal combustion engine using the fuel containing at least 1 sort (s) selected from the natural fats and oils, the hydrogenated process of a natural fats, the transesterification of a natural fats, and the hydrogenated process of the transesterification of a natural fats and oils,
A sulfur compound containing at least one -CSC- bond in a base oil,
Lubricating oil composition, characterized in that the sulfur contained in the -CSC- bond is 0.3% by mass or less based on the total amount of the composition. 제1항에 있어서, 상기 황 화합물이 -C-Sx-C- 결합(x는 2 이상의 정수임)을 포함하지 않는 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition of claim 1, wherein the sulfur compound does not include a -CS x -C- bond (x is an integer of 2 or more). 제1항 또는 제2항에 있어서, 알칼리 토류 금속계 청정제가 0.35 질량％ 이하 배합되어 있는 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition according to claim 1 or 2, wherein an alkaline earth metal-based detergent is blended at 0.35 mass% or less. 제1항 내지 제3항 중 어느 한 항에 있어서, 인 함유량이 조성물 기준으로 0.12 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition according to any one of claims 1 to 3, wherein the phosphorus content is 0.12 mass% or less based on the composition. 제1항 내지 제4항 중 어느 한 항에 있어서, 황산 회분이 1.1 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition as described in any one of Claims 1-4 whose sulfuric acid ash content is 1.1 mass% or less. 제1항 내지 제5항 중 어느 한 항에 있어서, 페놀계 산화 방지제 및/또는 아민계 산화 방지제를 조성물 전량 기준으로 0.3 질량％ 이상 배합하는 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition according to any one of claims 1 to 5, wherein a phenolic antioxidant and / or an amine antioxidant are blended in an amount of 0.3% by mass or more based on the total amount of the composition. 제1항 내지 제6항 중 어느 한 항에 있어서, 황 함유량이 조성물 전량 기준으로 0.5 질량％ 이하인 것을 특징으로 하는 윤활유 조성물.The lubricating oil composition according to any one of claims 1 to 6, wherein the sulfur content is 0.5% by mass or less based on the total amount of the composition.
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